JPH11513719A - Preparation of non-foamed or foamed polyurethane elastomers based on polyisocyanate mixtures containing 3,3'-dimethylbiphenyl 4,4'-diisocyanate and isocyanate prepolymers suitable for this purpose - Google Patents

Abstract

  (57) [Summary] Compressible, preferably foamed polyurethane elastomers (hereinafter abbreviated as PU elastomers) based on a polyisocyanate mixture containing 3,3′-dimethylbiphenyl 4,4′-diisocyanate are a) relatively high molecular weight C. 3,3'-dimethylbiphenyl 4,4'-diisocyanate and tolylene diisocyanate, diphenylmethane diisocyanate At least one other organic diisocyanate selected from the group consisting of 1,2-diphenylethane diisocyanate and phenylene diisocyanate, and / or at least one aliphatic diisocyanate having 4 to 12 carbon atoms, and / or 6-18 carbon atoms It is advantageous to react at least one of the cycloaliphatic diisocyanates having here components (a), (c) and, depending on the use, (b) by a prepolymer method, which are reacted with d) catalysts, e) It is prepared by reacting in the presence or absence of a blowing agent, f) additives. Isocyanate prepolymers suitable for this purpose are preferably based on diphenylmethane 4,4'-diisocyanate and 3,3'-dimethylbiphenyl 4,4'-diisocyanate.

Description

DETAILED DESCRIPTION OF THE INVENTION Polyiso containing 3,3'-dimethylbiphenyl 4,4'-diisocyanate Production of non-foamed or foamed polyurethane elastomers based on cyanate mixtures Isocyanate prepolymer suitable for this purpose   The invention contains 3,3'-dimethylbiphenyl 4,4'-diisocyanate Non-foamed, preferably foamed polyurethane based on a polyisocyanate mixture Tan elastomer (hereinafter abbreviated as PU elastomer) a) a relatively high molecular weight polyhydroxyl compound and, if desired, b) a low molecular weight hydroxyl group-containing chain extender and / or a crosslinking agent, c) 3,3'-dimethylbiphenyl 4,4'-diisocyanate and tolylenedi Isocyanate, diphenylmethane diisocyanate, 1,2-diphenylethane Selected from the group consisting of diisocyanates and phenylene diisocyanates At least one other organic diisocyanate and / or 4 to 12 carbon atoms At least one aliphatic diisocyanate having at least one and / or 6 to 18 carbons At least one alicyclic diisocyanate having an elemental atom, wherein the component (a ), (C) and (b) depending on the use may be reacted by a prepolymer method. And these are d) a catalyst, e) a blowing agent, f) additives, For producing by reacting in the presence or absence of Isocyanate prepolymers, preferably diphenylmethane 4,4'- Diisocyanate (MDI) and 3,3'-dimethylbiphenyl 4,4'-dii It relates to a prepolymer based on soocyanate (TODI).   Microporous PU elastomers have excellent static and dynamic properties. Its unique system Due to vibration characteristics and long-term use characteristics, it is used especially in vibration and shock control systems.   The production of non-foamed or foamable, for example, microporous PU elastomers, has long been Was It was known from many patents and literature.   These are industrially important because of their good mechanical properties and low-cost processing. This is because it is advantageous. Different mixing of different types of chemically formable components Use by ratio may be thermoplastically processable or crosslinked if compressible. Or the production of foamed PU elastomers, which have a wide variety of Has processing behavior and mechanical properties. Overview of PU elastomers and their properties And uses, for example,Kunststoff-Handbuch, Volume 7, Polyurethane.1s t Edition, 1966, edited by Dr. R. Vieweg and Dr. A. Hoechtlen, 2nd E dition, 1983, edited by Dr. G. Oertel, and 3rd edition, 1993, edited by P rof.GW Becker and Prof.D.Braun, Carl-Hanser-Verlag, Munich , Vienna. Is shown in   Compared to rubber types that can be used in the same way, microporous PU elastomers It has volumetric compressibility and very good vibration damping properties, It is used as a component of a fire control system, especially in the automotive industry. Microporous Useful starting materials for making PU elastomers include naphthylene 1,5-di Isocyanate (1,5-NDI) and poly (ethylene) having an average molecular weight of 2000 Glycol adipic acid ester). These are fatty acid sulfones containing an activator in the form of an isocyanate prepolymer. Reacts with aqueous solutions of acid esters (Kunststoff-Handbuch. Volume 7, Polyu rethane, 1st Edition, Page 270 ff. ).   Its basic formulation has very good damping properties and static and dynamic performance parameters Since the production of PU elastomers with 1,5-NDI which gives the properties of Efforts to convert to diisocyanates that are easy to handle and cheap are isolated and disclosed It is just that. Because this significantly reduces the mechanical properties It is because it will be done. General compressible PU elastomer and microporous PU elastomer , Especially 1,5-NDI, tolylene diisocyanate (TDI) and 4,4 ' -The difference in characteristic properties from microporous PU elastomers based on MDI is:Journ al of Elastomers and Plastics, vol. 21 (1989), pages 100 to 121. Shown in And You. A significant disadvantage of microporous PU elastomers based on 4,4'-MDI is that As heating to the material increases and consolidation increases significantly under dynamic loading, This means that the degree of vibration damping becomes higher. The material wears out sooner than PU elastomers.   Despite these obvious disadvantages, 1,5-NDI has a low melting point and low cost To switch to 4,4'-MDI to produce microporous PU elastomers I have been. However, in these experiments, new starting components, especially comparative High molecular weight hydroxyl compounds improve mechanical properties of microporous PU elastomers Use is restricted.   EPA-A-0 496 204 (US-A-5 173 518)Has a relatively high molecular weight poly As hydroxyl compounds, condensed polyoxytes having an average molecular weight of 150 to 500 Polyether polycarbonate dio composed of ramethylene glycol units A method for producing a porous PU elastomer using a polymer is described. This is a comparison Even at very low temperatures, it improves the mechanical properties, especially the elongation at break. But At 70 ° C, which is known to correlate with dynamic compaction valuesDIN 53 572of No improvement in static compression set values can be confirmed. Polyisocyanate Average static compression set values, even when using 1,5-NDI Was just obtained.   Produce elastic, compressible or foamable PU or PU polyurea molded products To do so, for example, water is combined as a blowing agent, and 4,4′-MDI is used as a base material. To use pseudoprepolymersEP-B-0 243 83 2 (US-A-4 798 851) Have improved mechanical and hydrolytic properties To produce foam or compressible PU elastomers, containing ester groups, With the aim of obtaining a polyhydroxyl compound whose measurement has been made possible by As a relatively high molecular weight polyhydroxyl compound, short-chain polyoxytetra Uses hydroxyl-containing polycondensate from methylene glycol and aliphatic dicarboxylic acid It is described. Static or dynamic, depending on the means by which the anti-vibration material is characterized The details of permanent deformation under severe loads were not disclosed.   DE-A-36 13 961 (US-A-4 647 596)The polytetrahydraf A relatively high molecular weight polyhydrogen containing a copolymer of orchid and ε-caprolactone 4,4'-MDI based microporous PU based on defined components of xy compounds Disclosed are elastomers, which compromise static strength and dynamic stretch. Has mechanical properties. Expensive raw materials to produce polyhydroxyl compounds Despite the use of fees, the performance gain achieved is dependent on the test variable, namely Durability of product, flexural strength by Dematia method and permanent deformation at 50% compression Seems relatively small from a point of view. For example, directly to the actual important value of dynamic compaction For the compression set concerned, the measured value is Only a slight improvement.   In addition, the indicator of the test used, namely the durability of the product according to the Dematian method The properties and flexural strengths are, in particular, improved for some properties, for 4,4'-MDI substrates and And the true performance differences between 1,5-NDI based polyurethane elastomers. Cannot be described, it is sufficiently suitable for the evaluation of actual and accurate dynamic characteristics. I can't say. Therefore, the embodiment using 1,5-NDI as a base material is 4,4'-MDI It did not show a better level of characteristics than the example using the substrate as a base material.   The stepwise production of PU elastomers is also known.DE-A-25 47 864 ( US-A-4 191 818) According to an essentially linear relatively high molecular weight hydroxy Reaction of the compound with an excess amount of diisocyanate to give a hydroxyl group-containing additive. To produce an additive, followed by an excess of the symmetric aromatic diisocyanate And an alkanediol or di (alkylene glycol) as a chain extender To produce a heat-resistant PU elastomer. PU foam foam by this method When preparing tomers, the chain extender used is water and, if desired, an alcohol. Combination of diol and / or di (alkylene glycol) terephthalate You.   Foamed PU elastomer isDE-A-2 940 856 (US-A-4 334 033)Written in It can also be manufactured by the method described. According to this method, relatively high Organic diisocyanates with high molecular weight polyhydroxyl compounds and possible chain extenders And OH to NCO at a ratio of 1.2: 1 to 2: 1 to form a hydroxyl group-containing prepolymer. Generate. This is added to components (I) and (II) at a weight ratio of about 80-20: 20-80. Separate. Component (I) reacts with 1,5-NDI at a ratio of OH to NCO groups of 1: 2.5 to 12, An NDI-polyurethane additive containing O groups is produced and compound (II) is chain-extended. Combines with prolonging agents, water and additives to form mixture (II). NDI-polyurethane The additive and the mixture (II) react at the end to produce a foamed or non-foamed PU elastomer. To achieve. According to this method, the components can be accurately weighed, quickly and violently. Mixed. PU elastomers are uniform and have uniform mechanical properties throughout the molded article. It has nature. Based on a prepolymer containing isocyanate groups, Containing poly (ethanediol adipate), 2,4-TDI and TODI, And 2-chloroaniline-2,5-dichloroaniline-formaldehyde condensation Modifiable PU-polyurea prepolymer prepared from a compound-containing curing agent The ingredients areGB-A 1 141 323It is described in. PU-poly produced from this Although urea elastomers have excellent mechanical properties, Is a disadvantage.   It is an object of the present invention to completely or at least partially handle expensive TODIs. Compressible or can be replaced with easy and inexpensive organic diisocyanates It is an object of the present invention to provide a method for producing a microporous PU elastomer. Other Mechanical and dynamic properties of PU elastomers Properties are improved, or at least a TODI based elastomer Must be appropriate. Relatively high molecular weight polyhydroxy used Regardless of the compound, the microporous PU elastomer was based on 4,4-MDI Do not have significantly improved static and mechanical properties compared to PU elastomers Must be used, especially for the manufacture of vibration and shock control systems. In particular, it must have such compression set and dynamic consolidation values.   The purpose of this is to: a) use a relatively high molecular weight polyhydroxyl compound and optionally , b) a low molecular weight hydroxyl group-containing chain extender and / or a crosslinking agent, c) an organic polyisocyanate; d) a catalyst, e) a blowing agent, and f) additives, And in the presence or absence of the organic polyisocyanate used is 3, 3 ' -Dimethylbiphenyl 4,4'-diisocyanate and tolylene diisocyanate , Diphenylmethane diisocyanate, 1,2-diphenylethanediiso Another aroma selected from the group consisting of cyanates and phenylenediisocyanates At least one of group diisocyanates and / or having from 4 to 12 carbon atoms At least one aliphatic diisocyanate and / or 6 to 18 carbon atoms Polyurethane at least one alicyclic diisocyanate having It has been found that this is achieved by a method of making the mer.   According to a preferred embodiment, the PU elastomer comprises urethane groups and isocyanate. The addition polymerization product containing a phosphate group is a relatively high molecular weight polyhydroxyl compound. (B) and TDI, MDI, 1,2-diphenylethane diisocyanate (DIB DI) phenylene diisocyanate (PDI) and preferably 4,4'-MDI At least one aromatic diisocyanate selected from the group consisting of Is hexamethylene 1,6-diisocyanate (HDI) and / or 1-isocyanate Nato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IP DI) and the addition polymerization product is combined with the addition polymerization product in one step By reacting with TODI, which can react Produced by a prepolymer method that converts to a prepolymer containing anate groups You. The microporous PU elastomer is water or water and, if desired, a low molecular weight hydroxyl-containing Chain extender and / or crosslinking agent (b) and / or relatively high molecular weight polyhydroxy By reacting with a mixture with the sil compound (a), contains an isocyanate group From the prepolymer.   The present invention also contains isocyanate groups and preferably comprises 3.3 to 10% by weight. Or a prepolymer having an NCO content of 3.5 to 9.0 wt. At least one relatively high molecular weight polyhydroxyl compound (a) or (a) Mixing with at least one low molecular weight hydroxyl-containing chain extender and / or crosslinking agent (b) The aromatic diisocyanate selected from the group consisting of MDI, DIBDI and PDI At least one, preferably 4,4'-MDI and / or HDI and And / or containing IPDI, a urethane group and an isocyanate group, and Addition polymerization products having an NCO content of 8% by weight, preferably 1.2 to 7.5% by weight And the addition polymerization product is injected into the reaction mixture T which can react with the addition polymerization product in one step or, preferably, split It relates to a prepolymer prepared by reacting with ODI.   Urea in PU elastomers based on 1,5-NDI or TODI and / or The crystallinity of hard segments containing urethane groups is Anate, for example, with the combination of low cost 4,4 'MDI with bent structure One skilled in the art will appreciate that the resulting PU elastomer will be converted to an aromatic diisocyanate. It was inferred that the static and dynamic properties were inferior to the base one.   Thus, particularly selected aromatic, aliphatic and / or cycloaliphatic containing TODI Of microporous PU elastomers produced from diisocyanate mixtures Properties, almost comparable to elastomers made only from TODI, Also clearly compared with 4,4'-MDI based microporous PU elastomers Improved static and dynamic properties, especially compression set and dynamic set values, are expected. Did not. Therefore, the microporous PU elastomer produced by the method of the present invention is Lower cost than PU elastomers based on 1,5-NDI or TODI And, due to its good static and mechanical properties, vibration and shock control system Very useful for building. Furthermore, the reaction mixture is easy to handle and operate .   Compressible or preferably foamable, for example microporous, PU elastomers Starting materials (a) to (f) for the production of This will be described below. a) Suitable relatively high molecular weight polyhydroxyl compounds are advantageously at most trivalent , Preferably a divalent functional group, and, from 500 to 6,000, preferably from 800 to It has a molecular weight of 3,500, especially 1,000 to 3,300, and is preferably hydroxyl Group containing polymers such as polyacetals such as polyoxymethylene and especially water Insoluble formals such as polybutanediol formal and polyhexane All formal, polyoxyalkylene polyol such as polyoxybutylene Glycol, polyoxybutylene-polyoxyethylene glycol, polyoxy Butylene-polyoxypropylene glycol, polyoxybutylene-polyoxy Propylene-polyoxyethylene glycol, polyoxypropylene polyol And polyoxypropylene-polyoxyethylene polyol, and polyester Polyols such as organic dicarboxylic acids and / or dicarboxylic acid derivatives and divalent And / or from trihydric alcohols and / or dialkylene glycols Polyester polyols from xycarboxylic acids and lactones and also containing hydroxyl groups Contains polycarbonate.   It has been found to be very useful and therefore has a relatively high molecular weight The polyhydroxyl compound is at least 800 and up to 3,500, preferably 1,000 Having a molecular weight of ~ 3,300, and a polyester polyol, a hydroxyl group-containing poly Two members selected from the group consisting of carbonate and polyoxybutylene glycol It is an effective polyhydroxyl compound. Relatively high molecular weight polyhydroxyl compounds The substances can each be used alone or as a mixture.   Suitable polyoxyalkylene polyols are known in the art, for example, alkali gold. Genus hydroxides such as sodium or potassium hydroxide, or alkali metal alcohols Oxides such as sodium methoxide, sodium or potassium ethoxa Using iodide or potassium isopropoxide, and two to three, preferably Adds at least one initiator containing two reactive hydrogen atoms in a linked form By anionic polymerization carried out at room temperature or by a Lewis acid such as antimony pentachloride, fluorine. Boron etherate or the like or bleached clay as a catalyst, in the alkylene group From one or more alkylene oxides having 2 to 4 carbon atoms Prepared by on-polymerization.   Suitable alkylene oxides are, for example, 1,3-propylene oxide, 1, 2- or 2,3-butylene oxide, preferably ethylene oxide and 1, 2-propylene oxide and especially tetrahydrofuran. Alkyleneo The oxides may be used individually, alternately in succession, or as a mixture. Good Examples of suitable initiator molecules include water, organic dicarboxylic acids such as succinic acid, adipic acid, Phthalic acid and terephthalic acid, which have 1 to 4 carbon atoms, aliphatic and aromatic. An N-monoalkylated and N, N'-dialkylated diamine having an alkyl group; For example, monoalkylated and dialkylated ethyleneamine [sic], 1,3-p Ropylenediamine, 1,3- or 1,4-butylenediamine, 1,2-, 1 , 3-, 1,4-, 1,5- and 1,6-hexamethylenediamine, alkano Amines such as ethanolamine, N-methylethanolamine and N-ethyl Diethanolamine, dialkanolamines such as diethanolamine, N- Methyldiethanolamine and N-ethyldiethanolamine, and trialka Nolamines such as triethanolamine and ammonia. preferable Are dihydric and / or trihydric alcohols, for example 2 to 12 carbon atoms, preferably Alkanediols having 2 to 4 carbon atoms, such as ethanediol, 1 , 2- and 1,3-propanediol, 1,4-butanediol, 1,5-pen Tandiol, 1,6-hexanediol, glycerol and trimethylol Lopan, and dialkylene glycols such as diethylene glycol and dipro The use of pyrene glycol.   Preferably used polyoxyalkylene polyol has a molecular weight of 500 to 3, Polyoxybutylene glycol having a molecular weight of 000, preferably 650 to 2,300 (Polyoxytetramethylene glycol).   Other preferred polyhydroxyl compounds (a) are, for example, 2 to 12 carbon atoms. Alkanedicarboxylic acids having an atom, preferably an alkanedicarboxylic acid having 4 to 6 carbon atoms Candicarboxylic acid and / or aromatic dicarboxylic acid and polyhydric alcohol, preferably Alkanedio having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms And / or polyester polyols that can be prepared from dialkylene glycols It is. Examples of suitable alkanedicarboxylic acids are succinic acid, glutaric acid, adipate Acid, suberic acid, azelaic acid, sebacic acid and decanedicarboxylic acid. Suitable aromatic dicarboxylic acids are, for example, phthalic acid, isophthalic acid and terephthalic acid. Tar acid. Here, the alkanedicarboxylic acids can be used individually or mixed with each other. Then, any can be used. Instead of the free dicarboxylic acid, the corresponding dicar Derivatives of boric acid, for example dicarboxylic acids of alcohols having 1 to 4 carbon atoms Monoester or diester, or dicarboxylic anhydride can also be used You. Preferred is a mixture of succinic, glutaric and adipic dicarboxylic acids. Of the product, for example in a weight ratio of 20-35: 35-50: 20-32, and especially The use of dipic acid. Dihydric and polyhydric alcohols, especially alkanediol Or examples of dialkylene glycols are ethanediol, diethylene glycol, 1,2- or 1,3-propanediol, dipropylene glycol, 1,4-butane Tandiol, 1,5-pentanediol, 1,6-hexanediol, 1,1 0-decanediol, glycerol and trimethylolpropane. Preferred Ethanediol, diethylene glycol, 1,4-butanediol, 1 , 5-pentanediol, 1,6-hexanediol or specified diols Mixtures of at least two, especially 1,4-butanediol, 1,5-pentanedio And a mixture of 1,6-hexanediol. From lactone Polyester polyols such as ε-caprolactone, or hydroxycarboxylic Acids such as ω-hydroxycaproic acid can also be used.   To prepare polyester polyols, aromatic and / or aliphatic Bonic acid and preferably alkanedicarboxylic acids and / or their derivatives and polyvalent alkanes The coal in the absence of a catalyst or, preferably, in the presence of an esterification catalyst, Advantageously, under an atmosphere of an inert gas such as nitrogen, helium, argon, etc. In the molten state at 250 ° C., preferably between 180 and 220 ° C., advantageously below 10 The polycondensation is preferably carried out so that the acid value is preferably 2 or less. Preferred practice According to an embodiment, the esterification mixture at the above-mentioned temperature is provided with an acid number of 80 to 30, preferably Up to an acid number of from 40 to 30 at atmospheric pressure and subsequently up to 500 mbar, preferably Is polycondensed at 50-150 mbar. Suitable esterification catalysts include, for example, metals, Iron, cadmium, cobalt, lead, zinc, antimony in the form of metal oxides or salts; , Magnesium, titanium and tin catalysts. However, polycondensation also involves condensation water Diluents and / or entrainers for azeotropic distillation, such as benzene, toluene, It may be carried out in the liquid phase in the presence of xylene or chlorobenzene.   Organic Polycarboxylic Acids and / or Their Preparation to Prepare Polyester Polyols The derivative and the polyhydric alcohol are used in a molar ratio of 1: 1 to 1.8, preferably 1: 1.05. It is advantageous to polycondense at 1.2.   Polyester polyols that are preferably used include poly (alkanediol azide). Pate), for example, poly (ethanediol adipate), poly (1,4-butanegio) Adipate), poly (ethanediol-1,4-butanediol adipate) ), Poly (1,6-hexanediol-neopentyl glycol adipate) and And poly (1,6-hexanediol-1,4-butanediol adipate), and And polycaprolactone.   Other suitable polyester polyols are hydroxyl-containing polycarbonates. The hydroxyl group-containing polycarbonate is, for example, the above-mentioned alkanediol, , 4-butanediol and / or 1,6-hexanediol and / or dialki Ren glycols such as diethylene glycol, dipropylene glycol and di Butylene glycol can be used as a dialkyl or diaryl carbonate, e.g. Can be prepared by reacting with nyl carbonate or phosgene .   With respect to the hydroxyl-containing polypolycarbonate, the following are preferred. The use of a polyether polycarbonate diol that can be prepared by condensation. That is, a1) polyoxybutylene glycol having a molecular weight of 150 to 500, or a2) i) polyoxybutylene glycol having a molecular weight of 150 to 500 (a At least 10 mol%, preferably 50 to 95 mol% of 1);       ii) Unlike (a1), a molecular weight of 150 to 2,000, at least one kind Dialkylene glycol, at least one straight chain having 2 to 12 carbon atoms A chain or branched alkanediol and at least 5 to 15 carbon atoms And one kind of cyclic alkanediol [sic] or phosgene, diphenyl . Carbonate or C₁~ C_FourDialkyl carbonate having an alkyl group A mixture containing not more than 90 mol%, preferably 50 to 95 mol% of the mixture with b) A compressible or preferably foamed PU elastomer is produced by the process of the invention. To the relatively high molecular weight polyhydroxyl compound (a), if desired. A low molecular weight, hydroxyl group-containing bifunctional chain extender (b); Having, preferably a trifunctional or tetrafunctional crosslinking agent or a chain extender and a crosslinking agent Mixtures can also be used.   Such a chain extender and a crosslinking agent (b) are used for the mechanical properties of PU elastomer, Used to improve firmness. Suitable hydroxyl-containing chain extenders such as alkane All dialkylene glycol and polyoxyalkylene glycol, and hydroxyl Group-containing crosslinkers, such as tri- or tetrahydric alcohols and low-polymer polyoxymers The alkylene polyol has a functionality of 3 to 4, and is usually 800 or less, preferably It has a molecular weight of 18 to 400, in particular 60 to 300. 2 as chain extender Alkanes having 12 carbon atoms, preferably 2, 4 or 6 carbon atoms Diols such as ethanediol, 1,3-propanediol, 1,5-pentane Diol, 1,6-hexanediol, 1,7-heptanediol, 1,8- Octanediol, 1,9-nonanediol, 1,10-decanediol, In particular 1,4-butanediol and also dialkylenes having 4 to 8 carbon atoms Glycols such as diethylene glycol and dipropylene glycol and also Polyoxyalkylene glycol is used. However, branched and / or unsaturated Alkanediols having usually less than 12 carbon atoms, for example 1,2-pro Pandiol, 2-methylpropane-1,3-diol, 2,2-dimethylpro Pan-1,3-diol, 2-butyl-2-ethylpropane-1,3-diol But-2-en-1,4-diol and but-2-yne-1,4-diol, Diesters of terephthalic acid with alkanediols having 2 to 4 carbon atoms For example, bis (ethylene glycol) terephthalate or bis (1,4-butyl) Tandiol) terephthalate and hydroquinone or resorcinol Droxyalkylene ethers such as 1,4-di (β-hydroxyethyl) high Using droquinone or 1,3-di (β-hydroxyethyl) resorcinol Is preferred.   At least a trifunctional crosslinking agent which can be advantageously used in the production of PU cast elastomers Examples of trihydric and trihydric alcohols such as glycerol, tri Methylol propane, pentaerythritol and trihydroxycyclohexane And also low-polymer polyoxyalkylenepolyols having a functionality of 3-4. It is.   Suitable chain extenders and crosslinking agents (b) for the purposes of the present invention are each individually or in mixtures. Used in form. A mixture of a chain extender and a crosslinking agent can also be used.   In order to control the hardness of the PU elastomer, it is necessary to mix the components (a) and (b). It is better to change the mixing ratio in a relatively wide range, and to extend the bifunctional chain in PU elastomer. As the agent and at least the trifunctional crosslinking agent are increased, the hardness increases. Depending on the desired hardness Thus, the required amounts of components (a) and (b) can be measured experimentally in a simple manner. 5 to 50% by weight of the chain, based on the weight of the relatively high molecular weight polyhydroxyl compound An extender and / or a cross-linking agent, preferably 30 to 50% by weight of hard PU elastomer -It is advantageously used for production.   According to the invention, for the production of compressible and preferably microporous PU elastomers, One uses two organic polyisocyanates, one being TODI. TODI Used as an aromatic diisocyanate different from tolylene diisocyanate Salts such as 2,4- and 2,6-TDI and commercial mixtures, diphenylmeth Tandiisocyanates such as 2,4 '-, 2,2'- and preferably 4, 4'-MDI and a mixture of at least two of the mentioned MDI isomers, 1,2-diphenyl Phenylmethane diisocyanate, e.g. 2,4 '-, 2,2'- and also preferred Or 4,4'-DIBDI and a mixture of at least two of the mentioned DIBDI isomers , Phenylene diisocyanate, preferably 1,4-PDI (p-phenylene diisocyanate) Isocyanate, PPDI). With its good operability and achievement with it 4,4'-MDI compresses due to the very good mechanical properties of the elastomer Combined with TODI for the production of porous and preferably microporous PU elastomers In addition, they are particularly preferably used. TODI vs. TDI, MDI, DIBDI and P The molar ratio of the aromatic diisocyanate selected from the group consisting of DI is static and For example, TODI vs. Yoshi without a significant change in dynamic characteristics The aromatic diisocyanate is 1: 0. 1-1: 10, preferably 1: 0. 11- It can vary from 1: 9, particularly preferably from 1: 1 to 1: 7. preferable When using a combination of TODI and 4,4'-MDI, TODI / 4 , 4'-MDI molar ratio is 1: 0. 1-1: 10, preferably 1: 0. 11-1 : 9, especially in the range from 1: 1 to 1: 7. Aroma The group diisocyanate may be melted alone and then mixed or Is mixed and then used as a melt for the production of PU elastomers Or inject a solid diisocyanate into a melt of another diisocyanate; Melts and dissolves in it. By the latter method, solid TODI (melting point 70 ° C.) , Usually injected into the melt of 4,4'-MDI and dissolved while melting.   Instead of aromatic diisocyanates or mixtures thereof, branched or preferred Preferably, in the linear alkylene group, 4 to 12 carbon atoms, preferably 4 to 6 carbon atoms An aliphatic diisocyanate having elemental atoms and / or foamable, preferably compressible Unsubstituted or alkyl-substituted cycloalkyl for the production of PU elastomers Alicyclic ring having 6 to 18 carbon atoms, preferably 6 to 10 carbon atoms in a kylene group It is also possible to use formula diisocyanates. Aliphatic Diisocyanates Examples are dodecane 1,12-diisocyanate, 2-ethylbutane 1,4-diene Socyanate, 2-methylpentane 1,5-diisocyanate, butane 1,4- Diisocyanates and preferably hexamethylene 1,6-diisocyanate (H DI). Examples of suitable cycloaliphatic diisocyanates are cyclohexane 1,3- Or 1,4-diisocyanate, hexahydrotoluene 2,4- or 2 , 6-diisocyanate, dicyclohexylmethane 4,4 '-, 2,4'-if Or 2,2'-diisocyanate and preferably 1-isocyanato-3,3, 5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocy Anate, IPDI).   However, the organic polyisocyanate (c) may be replaced with a prepolymer containing isocyanate groups. Embodiments which can be used in the form of limers are preferred. This includes, for example, TODI-containing Combining the diisocyanate melt with at least one relatively high molecular weight polyhydroxy Compound (a) or (a) and at least one low molecular weight hydroxyl group-containing chain extension Reacting with a prolonging agent and / or at least one hydroxyl-containing crosslinking agent (b), or The TODI-containing diisocyanate melt with at least one relatively high molecular weight Reacting with a polyhydroxyl compound (a), followed by at least one hydroxyl group-containing compound. It can be prepared by a sequential reaction of reacting with a chain extender and / or a crosslinking agent (b). .   However, at least one relatively high molecular weight polyhydroxyl compound (a) Part or all of (a) and at least one low molecular weight hydroxyl group-containing A part or all of the chain extender and / or the cross-linking agent (b) is used in TDI, MDI , DIBDI and PDI, preferably 4,4'-MDI. At least one aromatic diisocyanate and / or HDI and / or IPD I to form a urethane group, preferably a urethane group and an isocyanate group. To obtain an addition polymerization product containing 05-8. 0% by weight, preferably 1. 2 ~ 7. Having an NCO content of 5% by weight, which is reacted with TODI to give isocyanate Containing isocyanate groups prepared by obtaining a prepolymer containing groups It is preferred to use a prepolymer.   For preparing addition polymerization products containing urethane and isocyanate groups The component (a) and, if desired, (b) and (c) are replaced with (a) or (a) (B) hydroxyl group to aromatic diisocyanate TDI, MDI, DIBDI and I PDI, preferably 4-4'-MDI and / or HDI and / or IPDI The number of equivalents of soocyanate groups exceeding 1: 1 to 6, preferably 1: 1. 01-4 It is advantageous to use an amount such that Urethane and isocyanate groups The addition polymerization product contained is subsequently added once or several times, preferably 2 times. (A) or the hydroxyl group of (a) and (b) versus the isocyanate of TODI The molar ratio of the nate groups is 1: 0. 02-6, preferably 1: 0. 1-5, especially 1: 0 . By reacting with an amount of TODI that can react to a few Converted to prepolymer containing anate groups.   As already pointed out, the isocyanate group-containing prepolymer is obtained by combining (a) and (b) It can be prepared using a mixture. However, according to a preferred embodiment, Isocyanate group-containing prepolymers are relatively high molecular weight polyhydroxyl compounds (A) with polyisocyanate (c), preferably 4,4'-MDI and TOD Prepared only by reacting with I. Particularly suitable for this purpose are polyethers. Sterol polyol, hydroxyl-containing polycarbonate and polyoxytetramethylene 500 to 6,000, preferably 800, selected from the group consisting of glycols More than 3,500, and especially from 1,000 to 3,300 molecular weight Is a bifunctional polyhydroxyl compound having   When 4,4'-MDI and TODI are used as aromatic diisocyanates , (A) and (b) hydroxyl groups, preferably (a) only hydroxyl groups 4,4'-MD I NCO groups to TODI NCO groups greater than 1: 1 to 6: 0. 02-6 It has been found useful to use the equivalence ratio.   Isoforms which can be used in accordance with the invention and which are preferably prepared by variations of the above method The cyanate group-containing prepolymer is used in an amount of 3. 3 to 10% by weight, good Preferably 3. It is advantageous to have an isocyanate content of 5 to 9% by weight.   Relatively high molecular weight to prepare prepolymers containing isocyanate groups Polyhydroxyl compound (a) or (a) and a low molecular weight hydroxyl group-containing chain extension The mixture with the prolonging agent and / or the crosslinking agent (b) is, for example, a TODI-containing aromatic diiso- In the form of a cyanate mixture, or preferably, TDI, MDI, DIBDI and At least one aromatic diisocyanate selected from the group consisting of PDI; Preferably, at the first stage used before processing with 4,4'-MDI and TODI , Organic polyisocyanate (c) at 80 to 160 ° C., preferably 110 to 1 The reaction is preferably performed at 50 ° C.   Thus, for example, the total amount of TODI or, if desired, a portion thereof is aromatic diisocyanate. , Preferably soluble in 4,4'-MDI, e.g. heating to 110C And a polyhydroxyl compound (a) heated to, for example, 125 ° C. Optionally, a hydroxyl group-containing chain extender and / or a crosslinking agent (b) may be Can be converted to a mixture. The maximum reaction temperature, usually in the range of After passing, any remaining portion of the TODI is added and a cooling step, eg, 120 React at ~ 130 ° C.   According to another preferred variant, component (a) or a mixture of (a) and (b) is used. The compound is heated, for example, to 140 ° C., at this temperature, for example, an aromatic diisocyanate, Preferably, the entire amount of 4,4′-MDI heated to 50 ° C. is added. 4, Immediately after the addition of 4'-MDI, inject the entire amount of TODI or May be divided and added gradually. Immediately after the addition of 4,4'-MDI, the TODI Advantageously injecting part and injecting the other part into the reaction mixture during the cooling stage Was found.   After the isocyanate content reaches the theoretical calculated value, the reaction is stopped. This includes A reaction time in the range of usually 15 to 200 minutes, preferably 40 to 150 minutes is required.   The isocyanate-containing prepolymer can be prepared in the presence of a catalyst. However, A soocyanate-containing prepolymer was prepared in the absence of a catalyst, which was It can also be injected into the reaction mixture for the production of the mer. d) The catalyst (d) used comprises a component (a) and, if used, a hydroxyl group which is also (b). An advantageous compound that strongly promotes the reaction between organic compounds and polyisocyanate (c) is there. Suitable catalysts are organometallic compounds, preferably organotin compounds, such as organic Tin (II) salts of carboxylic acids, such as tin (II) acetate, tin (II) octoate , Tin (II) ethylhexanoate and tin (II) laurate; Dialkyltin (IV) salts of organic carboxylic acids, such as dibutyltin diacetate, Dibutyltin dilaurate, dibutyltin malate and dioctyltindia It is a acetate. The organometallic compound can be used alone or, preferably, with a strongly basic amine. Use in combination. Examples which may be mentioned are amidines, for example 2,3-dimethyl-3. 4,4,5,6-tetrahydropyrimidine and tertiary amines such as triethyl Amine, tributylamine, dimethylbenzylamine, N-methylmorpholine , N-ethylmorpholine, N-cyclohexylmorpholine, N, N, N ', N'-tetraalkylalkylenediamine such as N, N, N', N'-te Tramethylethylenediamine, N, N, N ', N'-tetramethylbutanediamine Or N, N, N ', N'-tetramethylhexanediamine, pentamethyl Diethylenetriamine, bis (dimethylaminoethyl) ether, bis (dimethyl Laminopropyl) urea, 1,4, -dimethylpiperazine, 1,2-dimethyl Imidazole, 1-azobicyclo [3. 3. 0] octane and preferably 1 , 4-diazobicyclo [2. 2. 2] octane and alkanolamine compounds For example, triethanolamine, triisopropanolamine, N-methyldiethanol Nolamine and N-ethyldiethanolamine, and dimethylethanol Amine. Weight of components (a), (c) and (b) depending on use On the other hand, 0. 001 to 3% by weight, especially 0.1% by weight. 01 to 1 layer It is preferred to use the amount%. e) According to the method of the invention, a compressible PU elastomer such as a PU cast elastomer Is manufactured in the absence of water and physically or chemically acting blowing agents. Wear. However, the method is preferably a foamable, preferably microporous PU elastomer. Also used in the production of tomers. For this purpose, water is used as blowing agent (e) This is in situ organic polyisocyanate and preferably isocyanate groups Reacts with the containing prepolymer (a) to generate carbon dioxide gas and amino groups, It then reacts with the isocyanate prepolymer to obtain urea groups, thus extending the chain. It works as an agent.   Component (a) and, depending on use, (b) are due to the preparation and / or chemical structure Then, since it contains water, depending on the component (a) and use in some cases, ( It is not necessary to add water separately to b) or to the reaction mixture. But the desired bulkiness If additional water must be included in the polyurethane formulation to obtain This is usually 0.1% based on the weight of components (a) to (c). 001-3. 0% by weight, Preferably 0. 01-2. 0% by weight and especially 0.1% 2-1. Used in an amount of 2% by weight I do.   As the foaming agent (e), instead of water, or in combination with water, It evaporates under the action of the polymerization reaction, and is advantageously at -40 to 120 ° C. at atmospheric pressure. Preferably a low boiling liquid having a boiling point in the range of 10 to 90 ° C. or physically acting It is also possible to use gas as a blowing agent or as a chemically acting blowing agent. it can.   Gases suitable as liquids and blowing agents of the type described above are, for example, alkanes, e.g. Propane, n- and iso-butane, n- and iso-pentane and Or industrial pentane mixtures, cycloalkanes and cycloalkenes, for example Cyclobutane, cyclopentene, cyclohexene and preferably cyclopentane And / or cyclohexane, dialkyl ethers such as dimethyl ether, methyl Ethyl ether, diethyl ether, tert-butyl methyl ether, cycle Loalkylene ethers such as furan, ketones such as acetone, methyl ethyl keto , Acetals and / or ketals such as formaldehyde dimethyl acetate 1,3-dioxolane, acetone dimethyl acetal, carboxylic acid Ster eg ethyl acetate, methyl formate and tertiary butyl ethylene acrylate Tertiary alcohol, eg tert-butanol, decomposes in the troposphere, damaging the ozone layer No fluoroalkanes such as trifluoromethane, difluoromethane, Fluoroethane, tetrafluoroethane, and tetrafluoroethane and heptaph Fluoroethane, chloroalkanes such as 2-chloropropane, and gases such as nitrogen , Carbon dioxide and noble gases such as helium, neon and krypton, and chemical Foaming agents which act in a similar manner to water, such as formic acid, acetic acid and propionic acid You can choose from.   Suitable as a foaming agent (e), preferred among liquids inert to NCO groups Are alkane with 4 to 8 carbon atoms, cyclo with 4 to 6 carbon atoms Alkanes or alkanes and cycloalkanes have a boiling point at atmospheric pressure of -40 to 50. It is a mixture that is in ° C. Particularly preferred are (cyclo) alkanes of C5 such as n -Pentane, iso-pentane and cyclopentane and their industrial mixtures It is.   Other suitable blowing agents are salts which decompose thermally, such as ammonium bicarbonate, ammonium And ammonium salts of organic carboxylic acids such as malonic acid, It is a monoammonium salt of uric acid, formic acid or acetic acid.   Alone or in the form of a mixture, for example a liquid mixture, a gas mixture or a gas and liquid The most advantageous of solid blowing agents, low-boiling liquids and gases which can be used in any mixture of The exact amount depends on the density to be obtained and the amount of water used. The desired amount is easy with a simple test Can decide. In each case, the components (a) and (c) and (b) With respect to the weight of 5 to 35 parts by weight, preferably 2 to 15 parts by weight of solids, 1 -30 to 30 parts by weight of liquid, preferably 3 to 18 parts by weight, and / or 0. 01-8 With an amount of gas of 0 parts by weight, preferably 10 to 35 parts by weight, usually satisfactory results are obtained. Fruit is obtained. Gases such as air, carbon dioxide, nitrogen and / or helium are charged Through a relatively high molecular weight, hydroxyl-containing chain extender and / or crosslinker (b), Or through polyisocyanate (c) or (a), (c) and This is performed through (b) depending on the application.   The blowing agents not used are, as indicated above, all halogenated chlorofluorocarbons. Locarbon. f) If desired, additive (f) is also a compressible, preferably foamable PU elastomer. May be included in the reaction mixture for the production of Examples that may be mentioned are surfactants, air bubbles. For stabilizers, air conditioners, fillers, flame retardants, nucleating agents, antioxidants, stabilizers, and lubricants Release agents, dyes and pigments.   Suitable surface-active substances are, for example, compounds which help to promote the homogeneity of the starting materials. It is also suitable for adjusting the ejection and bubble structure. Examples which may be mentioned are emulsifiers such as castor Oil sulfate or sodium salt of fatty acid and amine salt of fatty acid, for example Ricinoleic acid diethanolamine salt, sulfonate such as dodecylbenze Of di- or dinaphthylmethane disulphonic acid and ricinoleic acid Potassium metal or ammonium salts, foam stabilizers such as siloxane-oxo Sialkylene copolymers and other organopolysiloxanes, epoxidized alkyls Phenol, ethoxylated fatty alcohol, paraffin oil, castor oil or Sinolates, funnel oils and peanut oils, and foam regulators, such as For example, paraffin, fatty alcohol and dimethylpolysiloxane. As a side group Low-polymer polyacrylate having polyoxyalkylene group and fluoroalkane group They are also suitable for improving the emulsifying action, the cell structure and / or their stability. The surface-active substance usually comprises 10% of a relatively high molecular weight polyhydroxyl compound (a). 0 parts by weight, 0. It is used in an amount of from 01 to 5 parts by weight.   For the purposes of the present invention, fillers, in particular reinforcing fillers, are known per se and are customary fillers. And inorganic fillers, reinforcing agents and extenders. Unique example is inorganic filler example For example, siliceous minerals such as layered silicates such as antigorite, serpentine, hornb Lend, amphibole, warm asbestos, talc, metal oxides such as kaolin, aluminum oxide Minium, aluminum silicate, titanium oxide and iron oxide, metal salts such as chalk Barite and inorganic pigments such as cadmium sulfide, zinc sulfide and glass particles. Suitable organic fillers are, for example, carbon black, melamine, expanded graphite , Rosin, cyclopentadienyl resin and graft polymer.   As reinforcing fillers, preference is given to fibers, for example carbon fibers or especially glass Fibers, especially when high heat distortion resistance or very high stiffness is required. Is coated with a coupling agent and / or a sizing agent. Suitable Gala Fiber is [lacuna], such as glass fiber fabric, glass mat , Glass non-woven fabric and / or preferably 5 to 200 μm in diameter, preferably 6 to 1 Glass fiber roving or chop of low alkali E glass having 5 μm Used in the form of toglass fiber and generally incorporated into the composition of the molded article, 0. 0,5 to 1 mm, preferably 0,1 mm. 1-0. It has an average fiber length of 5 mm.   Inorganic and organic fillers can be used alone or as a mixture and are usually reactive. The mixture is added in an amount of 0.1 to the weight of the components (a) to (c). 5-50% by weight, preferred Or 1 to 30% by weight.   Suitable flame retardants are, for example, tricresyl phosphate, tris (2-chloro Ethyl) phosphate, tris (2-chloropropyl) phosphate, tri (1,3-dichloropropyl) phosphate, tris (2,3-dibromoprop) Ropyl) phosphate and tetrakis (2-chloroethyl) ethylenediphospho Fate.   Apart from the halogen-substituted phosphates mentioned above, the flame retardant of the present invention In order to make the PU elastomer to be produced, inorganic flame retardants such as red phosphorus, hydrated oxidation Aluminum, antimony trioxide, arsenic trioxide, ammonium polyphosphate and sulfur Calcium or cyanuric acid derivatives such as melamine or at least two flame retardants For example, a mixture of ammonium polyphosphate and melamine, and also Starch and / or expanded graphite can be used. Generally, any In some cases, the specified flame retardant or mixture is used per 100 parts by weight of the components (a) to (c). It is advantageous to use 5 to 50 parts by weight, preferably 5 to 25 parts by weight of Was found.   Nucleating agents that can be used are, for example, talc, calcium fluoride, sodium phenyl With phosphinate, aluminum oxide and finely divided polytetrafluoroethylene Can be used in an amount of 5% by weight based on the total weight of the components (a) to (c). You.   Suitable antioxidants and heat stabilizers that can be added to the PU elastomer of the present invention include: For example, halides of metals of Group I of the periodic table, such as sodium halide, potassium Lithium, optionally copper (I) halides, such as chloride, bromide or In combination with iodides, sterically hindered phenols, hydroquinones, and And substituted compounds of these groups, and mixtures thereof, which are preferably Is used at a concentration of 1% by weight or less based on the weight of the components (a) to (c).   Examples of UV stabilizers include various substituted resorcinols, salicylates, benzotris Azoles and benzophenones and also sterically hindered amines are Generally, based on the weight of the components (a) to (c), 2. Used in amounts less than 0% by weight You.   Lubricants and release agents are generally similar to the weight of components (a)-(c). Stearic acid, stearyl alcohol, stearyl Esters and fatty acid esters of stearamide and pentaerythritol It is.   In addition, organic colorants such as nitrosine, pigments such as titanium dioxide, cadmium sulfide , Cadmium selenide sulfide, phthalocyanine, ultramarine blue or Carbon black can be added.   Details of other conventional auxiliaries and additives mentioned above can be found in expert literature, for exampleth e monograph by J.M. H. Saunders and K.S. C. Frisch "High Polymers", VolumeXVI, Poly urethanes, parts 1 and 2 Interscience Publishers 1962 and 1964, or Kunstst off-Handbuch, Polyurethane, Volume VII, C arl-Hanser-Verlag, Munich, Vienna, 1st, 2nd and 3rd Editions, 1966, 1983 and 1 993. It is out in   For the production of compressible or preferably foamed PU elastomers, relatively high Molecular weight of the polyhydroxyl compound (a), if desired, a low molecular weight chain extender and / or Or a crosslinking agent (b) and, if desired, a chemically acting blowing agent, preferably water, In the presence or absence of catalyst (d), blowing agent (e) of physical action and additive (f) Containing an organic polyisocyanate (c) or preferably an isocyanate group, And from (a), (b) and (c), or preferably (a) and (c) ) And a prepolymer prepared from a hydroxyl-containing chain extender and / or a crosslinking agent (b) And a mixture of a part of (a) and (b) and a part of (a), (b) and water A mixture, or preferably a mixture of (b) and water or water, and a polyisocyanate (C) or the NCO groups of the prepolymer containing isocyanate groups versus the component (a) Depending on the use, (b) and also, depending on the use, the reactivity of the foaming agent which acts chemically A hydrogen atom equivalent ratio of 0.8 to 1.2: 1, preferably 0.95 to 1.15: 1, In particular, the reaction is performed in such an amount that the amount becomes 1.00 to 1.05: 1.   Compressible or, preferably, foamed PU elastomers can be prepared by methods described in the literature, for example, Manufactured by a one-shot method or preferably a prepolymer method using a known mixing device. Can be built.   In order to produce a compressible PU elastomer, the starting material must be free of blowing agent (e). In the presence, usually uniformly mixed at 80-160 ° C, preferably 110-150 ° C. The reaction mixture is poured into an open, heated or unheated mold and allowed to cure. In order to produce a foamable PU elastomer, the components are likewise a blowing agent, preferably Or mixed in the presence of water and poured into a heated or unheated mold. The mixture After placing in the mold, the mold is closed and the reaction mixture is added, for example, from 1.1 to 8, preferably. Or 1.2 to 6, especially 2 to 4 to form a molded article. There are enough molded products Immediately after the strength becomes sufficient, the release time depends, inter alia, on the mold temperature and mold It is usually in the range of 10 to 60 minutes, depending on the shape and the reactivity of the reaction mixture.   The compressible PU elastomer produced by the method of the present invention, when not containing a filler, 1.0 to 1.4 g / cm^Three, Preferably 1.1 to 1.25 g / cm^ThreeIs the density of , For filler-containing products, usually 1,2 g / cm^ThreeIt has the above density. Foaming PU elastomer is 0.2 to 1.1 g / cm^Three, Preferably 0.35 to 0.80 g / cm^ThreeIs the density of   The PU elastomer produced by the method of the present invention can be used for the production of molded articles, Used for machine construction and vehicle department. Foamable PU elastomers are particularly suitable for vibration damping and Manufacture of cushioning elements, e.g. for vehicles, especially automobiles, Suitable. Example Comparative Example I a) of 4,4'-MDI based prepolymers containing isocyanate groups Manufacture   1 having an average molecular weight of 2000 (calculated from the number of hydroxyl groups determined experimentally) 000 parts by weight (0.5 mol) of poly (ethanediol (0.5 mol) -1, 4-butanediol (0.5 mol) adipate (1 mol)) Heated to 0 ° C. and at this temperature 380 parts by weight (1.52 mol) heated to 50 ° C. , 4,4'-MDI with vigorous stirring.   This gives an NCO content of 6.19% by weight and 1600 mPa · s at 90 ° C. A prepolymer having a viscosity was obtained (the viscosity was measured in the following Comparative Examples and Examples). Measured using a Haake rotational viscometer, b) Production of foam molded products   The crosslinking component is 2,2 ', 6,6'-tetraisopropyldiphenylcarbodii. 20.7 parts by weight of amides, ethoxylation with an average of 9 ethylene oxide units 2.9 parts by weight of a mixture of oleic acid and ricinoleic acid₉~ C_FifteenArchi 3.8 monoethanolamine salt of n-alkylbenzenesulfonic acid having a benzyl group Parts by weight, 36.3 parts by weight of sodium salt of sulfated castor oil, 36.3 parts by weight of water, And 30% by weight of pentamethyldiethylenetriamine and 70% by weight of N-methyl- 0.03 parts by weight of a mixture with N '-(dimethylaminomethyl) -piperazine In.   100 weight prepared by the method described in Comparative Example Ia and heated to 90 ° C Parts of the isocyanate prepolymer with 3.42 parts by weight of the crosslinking component for about 8 seconds. Stir vigorously. The reaction mixture is introduced into a sealable metal mold heated to 80 ° C. Was sealed and the reaction mixture was cured. After 25 minutes, remove the microporous molding from the mold And further cured at 110 ° C. for 16 hours.   The reaction mixture was not processed into test springs for dynamic testing. Comparative Example II a) of a prepolymer containing isocyanate groups and based on 4,4'-MDI Manufacture   1000 parts by weight of poly (ethanediol-1,4-buta) described in comparative example I Diol adipate) and 3 parts by weight of trimethylolpropane 380 parts by weight (1.52 mol) of 4,4′-MDI heated to 50 ° C. The reaction was carried out in the same manner as in Comparative Example I.   This gives an NCO content of 5.80% by weight and 1750 mPa · s at 90 ° C. A prepolymer having a viscosity (measured using a rotational viscometer) was obtained. b) Production of foam molded products   100 parts by weight of the prepolymer of Comparative Example IIa and 3.1 parts by weight of the crosslinking component of Comparative Example Ib The parts by weight were used to produce a molded article in the same manner as in Comparative Example I. Comparative Example III a) Production of a prepolymer having an isocyanate group as a TODI base material   Instead of 4,4'-MDI, 290 parts by weight (1.097 mol) of 3,3'-MDI Dimethylbiphenyl 4,4'-diisocyanate (trizine diisocyanate ( Production of Comparative Example Ia was repeated, except that TODI)) was used.   This gives an NCO content of 3.76% by weight and 5100 mPa · s at 90 ° C. A prepolymer having a viscosity (measured using a rotational viscometer) was obtained. b) Production of foam molded products   100 parts by weight of the prepolymer of Comparative Example IIIa and the crosslinking component 2.0 of Comparative Example Ib 7 parts by weight were used to produce a molded article in the same manner as in Comparative Example I. These components The part is removed from the mold after a curing time of 40 minutes in the mold and Cured thermally for 6 hours. Example 1 a) A prepolymer containing isocyanate groups and based on 4,4'-MDI / TODI Manufacture of polymer   1 having an average molecular weight of 2000 (calculated from the number of hydroxyl groups determined experimentally) 00 parts by weight (0.5 mol) of poly (ethanediol (0.5 mol) -1,4 -Butanediol (0.5 mol) adipate (1 mol)) While heating to 0 ° C. and stirring vigorously, 190 parts by weight (0.76 mol) of 4,4 '-MDI was heated to 50 ° C and 100.5 parts by weight (0.38 mol) of solid T ODI was added and reacted. After a reaction time of about 30 minutes, urethane and isocyanate A polyaddition product having a catenate group and an NCO content of 4.1% by weight is obtained. The addition product was mixed with 100.5 parts by weight (0.38 mol) of solid TODI and 120 ° C. And cooled to 90 ° C. over about 40 minutes with stirring.   This gives an NCO content of 6.09% by weight and 4000 mPa · s at 90 ° C. A prepolymer having a viscosity (measured using a rotational viscometer) was obtained. b) Production of foam molded products   Based on 4,4'-MDI / TODI, heated to 90C and described in Example 1a 100 parts by weight of the isocyanate prepared according to the method described in 3.36 parts by weight of the cross-linking component produced by the method were mixed with vigorous stirring.   After a stirring time of about 8 seconds, the reaction mixture was introduced into a sealable metal mold heated to 80 ° C. , The mold was sealed and the reaction mixture was cured. After a curing time of 45 minutes in the mold The micro-foamed product was removed from the mold and thermally cured at 110 ° C. for 16 hours. Example 2 a) A prepolymer containing isocyanate groups and based on 4,4'-MDI / TODI Manufacture of polymer   1000 parts by weight (0.5 mol) of poly (ethanediol-1,4-butanediene) All adipic acid ester) was initially charged with 285 parts by weight (1.14 mol) of 4, 4'-MDI, then immediately mixed with 50 parts by weight (0.19 mol) of TODI Was.   After a reaction time of about 30 minutes, containing urethane and isocyanate groups, 5.18 The resulting polyaddition product having an NCO content of 5% by weight is added to a further 50 parts by weight (0.19 mol) of TODI at 110-120 ° C.   This gives an NCO content of 6.10% by weight and 2100 mPa · s at 90 ° C. A prepolymer having a viscosity (measured using a rotational viscometer) was obtained.   b) Production of foam molded products   Using the prepolymer of Example 2a and a method similar to Example 1b, the foamed product Was manufactured. Example 3 a) Precursors containing isocyanate groups and based on 4,4'-MDI / TODI Manufacture of polymer   50 parts by weight (0.19 mol) of solid TODI was heated to 110 ° C. It was dissolved in 5 parts by weight (1.14 mol) of 4,4'-MDI. As described in Example 1a 1000 parts by weight (0.5 mol) of poly (ethanediol) heated to 125 ° C. -1,4-butanediol adipate) in 7 minutes with stirring Over time, the solution was added in small portions.   After a reaction time of about 35 minutes in a temperature range of 145 to 120 ° C., the urethane And a polyaddition product having isocyanate groups and an NCO content of 5.2% by weight The polyaddition product was further combined with 50 parts by weight (0.19 mol) of solid TODI. Reacted. After a reaction time of 70 minutes, the reaction mixture was cooled to 90 ° C.   This gives an NCO content of 6.12% by weight and 2200 mPa · s at 90 ° C. A prepolymer having a viscosity (measured using a rotational viscometer) was obtained. b) Production of foam molded products   100 parts by weight of the prepolymer of Example 3a and prepared as described in Comparative Example Ib Using 3.38 parts by weight of the crosslinked agent component, the foamed product is treated in the same manner as in Example 1b Manufactured by. Example 4 a) Precursors containing isocyanate groups and based on 4,4'-MDI / TODI Manufacture of polymer   319 parts by weight (1.276 mol) of 4,4'-MDI and 34 parts by weight (0.1 Except using a 4,4'-MDI / TODI mixture with 29 mol) of TODI Repeated the production of Example 3. Containing urethane and isocyanate groups, . The resulting polyaddition product having an NCO content of 6% by weight is further treated with 34 parts by weight (0.4% by weight). 129 mol) of TODI.   This gives an NCO content of 6.20% by weight and 1700 mPa · s at 90 ° C. A prepolymer having a viscosity (measured using a rotational viscometer) was obtained. b) Production of foam molded products   100 parts by weight of the prepolymer of Example 4a and prepared as described in Comparative Example Ib Using 3.42 parts by weight of the obtained crosslinking agent component, the foamed product was prepared in the same manner as in Example 1b. Manufactured by the method. Example 5 a) 4,4'-MDI / TODI-based prepolymer containing isocyanate groups Manufacture of polymer   335 parts by weight (1.34 mol) of 4,4'-MDI and 25 parts by weight (0.09 5 mol) of 4,4'-MDI / TODI mixture with TODI The production of Example 3 was repeated.   Contains urethane and isocyanate groups and has an NCO content of 5.73% by weight The resulting polyaddition product is treated with 25 parts by weight (0.095 mol) of TODI. Was.   This gives an NCO content of 6.17% by weight and 1700 mPa · s at 90 ° C. A prepolymer having a viscosity (measured using a rotational viscometer) was obtained. b) Production of foam molded products   Prepared by 100 parts by weight of the prepolymer of Example 5a and the method described in Comparative Example Ib The foamed product was prepared in the same manner as in Example 1b, using 3.40 parts by weight of the crosslinked agent component. Manufactured by. Example 6 a) 4,4'-MDI / TODI-based prepolymer containing isocyanate groups Manufacture of polymer   Instead of poly (ethanediol-1,4-butanediol adipate) Have an average molecular weight of 2000 (calculated from the number of hydroxyl groups determined experimentally) 1000 parts by weight (0.5 mol) of poly (1,4-butanediol (1 mol ) -1,6-hexanediol (1 mol) adipate (2 mol)) Example 3 was repeated except that was used.   This gives an NCO content of 6.02% by weight and 2100 mPa · s at 90 ° C. A prepolymer having a viscosity (measured using a rotational viscometer) was obtained. b) Production of foam molded products   100 parts by weight of the prepolymer of Example 6a and 3.33 parts by weight of the crosslinking agent component of Comparative Example Ib The parts by weight were used to produce a foamed product in the same manner as in Example 1b.   Prepared by the method described in Comparative Examples Ib to IIIb and Examples 1b to 6b The static and dynamic mechanical properties of micro foamed PU elastomer Used for   The measured static mechanical properties are the tensile strength in DIN 53 571. Is the elongation at break in DIN 53 571 and in DIN 53 515 Spacer having a height of 18 mm and a 40 × 40 DIN 53 using a test sample having a base area of 30 mm and a height of 30 (1 mm height) Compression set at 80 ° C. according to the modified method of No. 572. Compression set ( CS) is the formula (Where H₀Is the original height (mm) of the test sample, H₁Is in the deformed state of the test sample. Height (mm) and H_TwoIs the height (mm) of the test sample after depressurization You. ).   The determined dynamic mechanical properties include displacement increase at maximum force (DI) and consolidation (CN). (Figure). In order to measure consolidation, the part was constricted into three segments ( construction and a height of 100 mm, an outer diameter of 50 mm, 10 A cylindrical test spring with an internal diameter of mm was produced. 6kN force and 1.2Hz After loading the spring at 100,000 duty cycles at a frequency, CN Is measured as the difference between the pre- and post-load height of the spring and recorded in percent . Consolidation is a measure of the permanent deformation of a foamed PU elastomer during periodic fatigue testing. is there. The lower this consolidation, the better the dynamic performance of the material.   The HR for the determination of the compaction after the dynamic test is determined by the characteristic line of the spring (cha). The measurement was carried out by recording the characteristic line. here, H₀Is the height before the load. 4th cycle at a pressure speed of 50 mm / min as the characteristic line Was recorded. 10 minutes later, H₁This is the height component after the characteristic line measurement It is. Shortly thereafter, the dynamic test was started.   After the dynamic test is completed, the HR is kept at 23 ° C. and 50% relative humidity for 24 hours. It is the height after the dynamic test, measured on a tube. Determining permanent consolidation after dynamic testing The reference point ((the height before measurement) used for Spring height H in new state₀And The dynamic test was performed in a room conditioned at 23 ° C. and 50% relative humidity, Performed without cooling work. The mechanical properties measured for the test sample are: Is summarized in the table.

[Procedure of Amendment] Article 184-8, Paragraph 1 of the Patent Act [Submission date] October 2, 1997 [Correction contents]                                The scope of the claims 1. a) Polyester polyol having a molecular weight of 800 to 6000, hydroxyl-containing polycarbonate -Carbonate and polyoxybutylene glycol, and, if necessary, b) a hydroxyl group-containing chain extender and / or crosslinking agent having a molecular weight of less than 800, c) an organic polyisocyanate; d) a catalyst, e) a blowing agent, and f) additives, And in the presence or absence of the organic polyisocyanate used is 3, 3 ' -Dimethylbiphenyl 4,4'-diisocyanate and further diphenylmethane di Isocyanate, 1,2-diphenylethane diisocyanate and phenylene Less of another aromatic diisocyanate selected from the group consisting of isocyanates Aliphatic diisocyanate having at least one and / or 4 to 12 carbon atoms And / or an alicyclic diisocyanate having 6 to 18 carbon atoms. A method for producing a polyurethane elastomer which is at least one kind of anate. 2. A relatively high molecular weight polyhydroxyl compound may have a functionality of 2-3, The method of claim 1 having a molecular weight of 6,000. 3. Relatively high molecular weight polyhydroxyl compounds are bifunctional, 800-3 The method of claim 1 having a molecular weight of 500. 4. A chain extender having a molecular weight of 800 or less, alkanediol, Selected from the group consisting of ethylene glycol and polyoxyalkylene glycol, The crosslinking agent has a molecular weight of 800 or less and has a trivalent or tetravalent alcohol and a functional group. Selected from the group consisting of oligomeric polyoxyalkylene polyols having a valency of 3-4. The method according to any one of claims 1 to 3, which is selected. 5. The organic polyisocyanate (c) used is 3,3'-dimethylbiphenyl 4 , 4'-diisocyanate, and tolylene diisocyanate, diphenylmeth Diisocyanate, 1,2-diphenylethane diisocyanate and phenyle Of another aromatic diisocyanate selected from the group consisting of At least one and / or hexamethylene 1,6-diisocyanate and / or Is 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclo 5. A liquid mixture of hexane according to any one of claims 1 to 4. The method described. 6. The organic polyisocyanate (c) used is 3,3'-dimethylbiphenyl 4 4,4'-diisocyanate and diphenylmethane 4,4'-diisocyanate The method according to any one of claims 1 to 4, wherein the method is a melt. 7. Organic polyisocyanate (c) is a prepolymer containing isocyanate groups And 3,3'-dimethylbiphenyl 4,4'-diisocyanate Anate, and also tolylene diisocyanate, diphenylmethane diisocyanate 1,2-diphenylethane diisocyanate and phenylene diisocyanate At least one other aromatic diisocyanate selected from the group consisting of An aliphatic and / or cycloaliphatic diisocyanate and at least one relatively high molecular weight And, if desired, a low molecular weight hydroxyl-containing linkage. 5. The composition according to claim 1, which is prepared from a chain extender and / or a crosslinking agent (b). The method according to any one of the preceding claims. 8. Organic polyisocyanate (c) is a prepolymer containing isocyanate groups Of a relatively high molecular weight polyhydroxyl compound (a) A part or all of (a) a low molecular weight hydroxyl group-containing chain extender and / or Represents a part or all of the mixture with the cross-linking agent (b), Cyanate, 1,2-diphenylethane diisocyanate and phenylenediiso At least one aromatic diisocyanate selected from the group consisting of cyanates And / or hexamethylene 1,6-diisocyanate and / or 1-isocyanate Reacts with nato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane To obtain an addition polymerization product containing a urethane group, and Reacting with methylbiphenyl 4,4'-diisocyanate to form an isocyanate group Claims 1 to 4 prepared by obtaining a prepolymer containing The method of any one of the preceding clauses. 9. The organic polyisocyanate (c) is a prepoly containing an isocyanate group. (A) a relatively high molecular weight polyhydroxyl compound used in the form of (A) and a low molecular weight hydroxyl group-containing chain extender and / or Alternatively, part or all of the mixture with the crosslinking agent (b) is By reacting with 4'-diisocyanate, an addition polymerization product containing a urethane group is obtained. And 3 and 3'-dimethylbiphenyl 4,4'-diisocyanate Prepared by reacting to obtain a prepolymer containing isocyanate groups The method according to any one of claims 1 to 4, wherein the method is performed. 10. The organic polyisocyanate (c) is a prepoly containing an isocyanate group. (A) a relatively high molecular weight polyhydroxyl compound used in the form of Or (a) and a low molecular weight hydroxyl group-containing chain extender and / or a crosslinking agent (b). The compound is tolylene diisocyanate, diphenylmethane diisocyanate, 1, 2-diphenylethane diisocyanate and phenylene diisocyanate Aromatic diisocyanates selected from the group consisting of -Diisocyanate and / or 1-isocyanato-3,3,5-trimethyl-5 -Isocyanatomethylcyclohexane, and (a) or the hydroxyl group of (a) and (b) Groups to isocyanate groups of the organic diisocyanate are reacted in an equivalent ratio of 1:> 1-6. To obtain an addition polymerization product containing urethane and isocyanate groups. (A) or the hydroxyl group of (a) and (b) versus 3,3'-dimethylbiphenyl The isocyanate group of 4,4'-diisocyanate is used in an equivalent ratio of 1: 0.02 to 6 and With 3,3'-dimethylbiphenyl 4,4'-diisocyanate, Claims prepared by converting to a prepolymer containing cyanate groups 5. The method according to any one of the ranges 1 to 4. 11. The organic polyisocyanate (c) is a prepoly containing an isocyanate group. (A) a relatively high molecular weight polyhydroxyl compound used in the form of Or (a) and a low molecular weight hydroxyl group-containing chain extender and / or a crosslinking agent (b). The compound is obtained by mixing diphenylmethane 4,4'-diisocyanate with a hydroxyl group The urethane groups are reacted at an equivalent ratio of 1:> 1 to 6 to form urethane and isocyanate groups. To obtain an addition polymerization product containing the same and (a) or (a) and (b) Hydroxyl group to 3,3'-dimethylbiphenyl 4,4'-diisocyanate 3,3'-dimethylbifu with isocyanate groups in an equivalent ratio of 1: 0.02 to 6 Prepolymers containing isocyanate groups with phenyl 4,4'-diisocyanate 5. A method according to claim 1, wherein said compound is prepared by conversion to a mer. The method of any one of the preceding claims. 12. The blowing agent (d) is an alkane having 4 to 8 carbon atoms, 4 to 6 carbon atoms Claim 1 selected from the group consisting of a cycloalkane having an atom and water. A method for producing a foamed polyurethane elastomer according to any one of claims 11 to 11 . 13. 2. The method according to claim 1, wherein the density of the elastomer is 0.2 to 1.1 g / l. 13. The method for producing a foamed polyurethane elastomer according to any one of items 12 to 12. 14.3.3 to 10% by weight NCO content and at least one relatively High molecular weight polyhydroxyl compound (a) or (a) and low molecular weight hydroxyl group-containing The mixture with the chain extender and / or the crosslinking agent (b) is treated with diphenylmethane diisocyanate. Nate, 1,2-diphenylethane diisocyanate and phenylenediisocyanate At least one aromatic diisocyanate selected from the group consisting of And / or hexamethylene 1,6-diisocyanate and / or 1-isocyanate -3,3,5-trimethyl-5-isocyanatomethylcyclohexane Containing urethane and isocyanate groups, and containing 0.05 to 8% by weight of NC An addition polymerization product having an O content is obtained, and this is treated with 3,3'-dimethylbiphenyl. And 4,4'-diisocyanate to form a prepolymer containing isocyanate groups. An isocyanate group-containing prepolymer prepared by obtaining a polymer. 15. (A) or the hydroxyl group of (a) and (b), diphenylmethane diisocyanate Nate, 1,2-diphenylethane diisocyanate and phenylenediisocyanate Aromatic diisocyanate selected from the group consisting of Tylene 1,6-diisocyanate and / or 1-isocyanato-3,3,5-to NCO group of 3,5-diisocyanatomethylcyclohexane The equivalent ratio of NCO groups of tylbiphenyl 4,4'-diisocyanate is 1:> 1 to 6 15. The isocyanate group-containing prepreg according to claim 14, which is 0.02 to 6. Rimmer. Having an NCO content of 16.3.3 to 10% by weight and at least one relatively High molecular weight polyhydroxyl compound (a) or (a) and low molecular weight hydroxyl group-containing The mixture with the chain extender and / or the crosslinking agent (b) is treated with diphenylmethane 4,4'- Reacted with diisocyanate to contain urethane and isocyanate groups, and To obtain an addition polymerization product having an NCO content of 0.05 to 8% by weight, and Reaction with 3,3'-dimethylbiphenyl 4,4'-diisocyanate gives Isocyanate prepared by obtaining a prepolymer containing cyanate groups A prepolymer containing a salt group. 17.3.3 to 10% by weight NCO content and polyester polyol , Hydroxyl-containing polycarbonate and polyoxytetramethylene glycol. Having a molecular weight of more than 800 and up to 3,500 selected from the group The polyhydroxyl compound is reacted with diphenylmethane 4,4'-diisocyanate To obtain an addition polymerization product containing urethane and isocyanate groups, and Reacting this with 3,3'-dimethylbiphenyl 4,4'-diisocyanate Prepared by obtaining a prepolymer containing isocyanate groups. Socyanate group-containing prepolymer. 18. (A) or the hydroxyl group of (a) and (b) versus diphenylmethane 4,4'-di NCO groups of isocyanate versus 3,3'-dimethylbiphenyl 4,4'-diisocy The equivalent ratio of NCO groups of anate is 1:> 1-6: 0.02-6. Item 18. An isocyanate group-containing prepolymer according to item 16 or 17.

────────────────────────────────────────────────── ─── Continuation of front page    (81) Designated countries EP (AT, BE, CH, DE, DK, ES, FI, FR, GB, GR, IE, IT, L U, MC, NL, PT, SE), UA (AM, AZ, BY) , KG, KZ, MD, RU, TJ, TM), AU, BG , BR, CA, CN, CZ, GE, HU, IL, JP, KR, LV, MX, NO, NZ, PL, RO, SG, S I, SK, TR, UA, US (72) Inventor Haselhorst, Walter             Germany, D-49088, Osnabrück,             Kurt-Thuoflsky-Stral             C, 5 (72) Inventors Jeske and Torsten             Germany, D-49152, Wehlendorf,             Ann, Dah, Budemühle, 1 (72) Inventors Bruns, Ute             Germany, D-49808, Lingen, Nahate             Igarenstrasse, 52 (72) Inventor Bormann, Heinz             Germany, D-49594, Alfhausen,             Haeker Strasse, 82 (72) Inventor Strauss, Michael             Germany, D-49448, Remfelde, Germany             Lünerweg, 10 (72) Inventor Scholz, Wolfgang             Germany, D-49448, Remfelde, Ga             Rutenstraße, 18 (72) Inventor Poker, Hartmut             Germany, D-49143, Bisendorf, Mo             Leweg, 1 (72) Inventor Felkel, Rüdiger             Germany, D-64625, Bensheim, Si             Janenbacher, Werk, 2 (54) [Title of the Invention] Polyisocyanate mixture containing 3,3'-dimethylbiphenyl 4,4'-diisocyanate                     Of non-foamed or foamed polyurethane elastomers based on material, and isoforms suitable for this purpose                     Cyanate prepolymer

Claims (1)

[Claims] 1. a) a relatively high molecular weight polyhydroxyl compound and, optionally, b) a low molecular weight hydroxyl group-containing chain extender and / or a crosslinking agent, c) an organic polyisocyanate; d) a catalyst, e) a blowing agent, and f) additives, And in the presence or absence of the organic polyisocyanate used is 3, 3 ' -Dimethylbiphenyl 4,4'-diisocyanate and further, tolylene diisocyanate , Diphenylmethane diisocyanate, 1,2-diphenylethanediiso Another aroma selected from the group consisting of cyanates and phenylenediisocyanates Having at least one aromatic diisocyanate and / or from 4 to 12 carbon atoms. At least one aliphatic diisocyanate and / or 6 to 18 carbon atoms Polyurethane at least one of alicyclic diisocyanates having at least one atom. The method of manufacturing the lastmer. 2. A relatively high molecular weight polyhydroxyl compound may have a functionality of 2-3, The method of claim 1 having a molecular weight of 6,000. 3. Relatively high molecular weight polyhydroxyl compounds are bifunctional, 800-3 Polyester polyol having a molecular weight of 500, and a hydroxyl group-containing polycarbonate Claims selected from the group consisting of carbonate and polyoxybutylene glycol The method of claim 1. 4. A chain extender having a molecular weight of 800 or less, alkanediol, Selected from the group consisting of ethylene glycol and polyoxyalkylene glycol, The crosslinking agent has a molecular weight of 800 or less and has a trivalent or tetravalent alcohol and a functional group. Selected from the group consisting of oligomeric polyoxyalkylene polyols having a valency of 3-4. The method according to any one of claims 1 to 3, which is selected. 5. The organic polyisocyanate (c) used is 3,3'-dimethylbiphenyl 4 , 4'-diisocyanate, tolylene diisocyanate, Tandiisocyanate, 1,2-diphenylethanediisocyanate and phenyl Another aromatic diisocyanate selected from the group consisting of diisocyanates At least one and / or hexamethylene 1,6-diisocyanate and / or Is 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclo 5. A liquid mixture of hexane according to any one of claims 1 to 4. The method described. 6. The organic polyisocyanate (c) used is 3,3'-dimethylbiphenyl 4 4,4'-diisocyanate and diphenylmethane 4,4'-diisocyanate The method according to any one of claims 1 to 4, wherein the method is a melt. 7. Organic polyisocyanate (c) is a prepolymer containing isocyanate groups And 3,3'-dimethylbiphenyl 4,4'-diisocyanate Anate, and also tolylene diisocyanate, diphenylmethane diisocyanate 1,2-diphenylethane diisocyanate and phenylene diisocyanate At least one other aromatic diisocyanate selected from the group consisting of An aliphatic and / or cycloaliphatic diisocyanate and at least one relatively high molecular weight And, if desired, a low molecular weight hydroxyl-containing linkage. 5. The composition according to claim 1, which is prepared from a chain extender and / or a crosslinking agent (b). The method according to any one of the preceding claims. 8. Organic polyisocyanate (c) is a prepolymer containing isocyanate groups Of a relatively high molecular weight polyhydroxyl compound (a) A part or all of (a) a low molecular weight hydroxyl group-containing chain extender and / or Can be used to transfer a part or all of the mixture with the crosslinking agent (b) to tolylene diisocyanate. G, diphenylmethane diisocyanate, 1,2-diphenylethane diisocyanate Aromatic diiso selected from the group consisting of At least one cyanate and / or hexamethylene 1,6-diisocyanate And / or 1-isocyanato-3,3,5-trimethyl-5-isocyanato Reaction with methylcyclohexane to obtain an addition polymerization product containing a urethane group And reacting it with 3,3'-dimethylbiphenyl 4,4'-diisocyanate. To obtain a prepolymer containing isocyanate groups. The method according to any one of claims 1 to 4, which is produced. 9. Organic polyisocyanate (c) is a prepolymer containing isocyanate groups Of a relatively high molecular weight polyhydroxyl compound (a) A part or all of (a) a low molecular weight hydroxyl group-containing chain extender and / or Represents a part or all of the mixture with the crosslinking agent (b), Reaction with '-diisocyanate to obtain an addition polymerization product containing a urethane group. And reacting it with 3,3'-dimethylbiphenyl 4,4'-diisocyanate. Prepared by obtaining a prepolymer containing isocyanate groups. The method according to any one of claims 1 to 4, wherein the method comprises: 10. The organic polyisocyanate (c) is a prepoly containing an isocyanate group. (A) a relatively high molecular weight polyhydroxyl compound used in the form of Or (a) and a low molecular weight hydroxyl group-containing chain extender and / or a crosslinking agent (b). The compound is tolylene diisocyanate, diphenylmethane diisocyanate, 1, 2-diphenylethane diisocyanate and phenylene diisocyanate Aromatic diisocyanates selected from the group consisting of -Diisocyanate and / or 1-isocyanato-3,3,5-trimethyl-5 -Isocyanatomethylcyclohexane, and (a) or the hydroxyl group of (a) and (b) Groups to isocyanate groups of the organic diisocyanate are reacted in an equivalent ratio of 1:> 1-6. To obtain an addition polymerization product containing urethane and isocyanate groups. (A) or the hydroxyl group of (a) and (b) versus 3,3'-dimethylbiphenyl The isocyanate group of 4,4'-diisocyanate is used in an equivalent ratio of 1: 0.02 to 6 and With 3,3'-dimethylbiphenyl 4,4'-diisocyanate, Claims prepared by converting to a prepolymer containing cyanate groups 5. The method according to any one of the ranges 1 to 4. 11. The organic polyisocyanate (c) is a prepoly containing an isocyanate group. (A) a relatively high molecular weight polyhydroxyl compound used in the form of Or (a) and a low molecular weight hydroxyl group-containing chain extender and / or a crosslinking agent (b). The compound is obtained by mixing diphenylmethane 4,4'-diisocyanate with a hydroxyl group The reaction is carried out at an equivalent ratio of 1:> 1 to 6 to form urethane and isocyanate. To obtain an addition polymerization product containing a thiol group, and to obtain (a) or (a) and ( b) hydroxyl group to 3,3'-dimethylbiphenyl 4,4'-diisocyanate When the equivalent ratio of the cyanate group is 1: 0.02 to 6,3,3′-dimethylbiphenyl is used. Prepolymers containing isocyanate groups with benzyl 4,4'-diisocyanate Any one of claims 1 to 4 which is prepared by converting The method of claim 1. 12. The blowing agent (e) is an alkane having 4 to 8 carbon atoms, 4 to 6 carbon atoms Claim 1 selected from the group consisting of a cycloalkane having an atom and water. A method for producing a foamed polyurethane elastomer according to any one of claims 11 to 11 . 13. 2. The method according to claim 1, wherein the density of the elastomer is 0.2 to 1.1 g / l. 13. The method for producing a foamed polyurethane elastomer according to any one of items 12 to 12. 14.3.3 to 10% by weight NCO content and at least one relatively High molecular weight polyhydroxyl compound (a) or (a) and low molecular weight hydroxyl group-containing The mixture with the chain extender and / or the crosslinking agent (b) is treated with diphenylmethane diisocyanate. Nate, 1,2-diphenylethane diisocyanate and phenylenediisocyanate At least one aromatic diisocyanate selected from the group consisting of And / or hexamethylene 1,6-diisocyanate and / or 1-isocyanate -3,3,5-trimethyl-5-isocyanatomethylcyclohexane Containing urethane and isocyanate groups, and containing 0.05 to 8% by weight of NC An addition polymerization product having an O content is obtained, and this is treated with 3,3'-dimethylbiphenyl. And 4,4'-diisocyanate to form a prepolymer containing isocyanate groups. An isocyanate group-containing prepolymer prepared by obtaining a polymer. 15. (A) or the hydroxyl group of (a) and (b), diphenylmethane diisocyanate Nate, 1,2-diphenylethane diisocyanate and phenylenediisocyanate Aromatic diisocyanate selected from the group consisting of Tylene 1,6-diisocyanate and / or 1-isocyanato-3,3,5-to NCO group of 3,5-dimethyl-5-isocyanatomethylcyclohexane The equivalent ratio of NCO groups of tylbiphenyl 4,4'-diisocyanate is 1:> 1 to 6 The isocyanate group-containing prepoly according to claim 14, which is 0.02 to 6. Ma. Having an NCO content of 16.3.3 to 10% by weight and at least one relatively High molecular weight polyhydroxyl compound (a) or (a) and low molecular weight hydroxyl group-containing The mixture with the chain extender and / or the crosslinking agent (b) is treated with diphenylmethane 4,4'- Reacted with diisocyanate to contain urethane and isocyanate groups, and To obtain an addition polymerization product having an NCO content of 0.05 to 8% by weight, and Reaction with 3,3'-dimethylbiphenyl 4,4'-diisocyanate gives Isocyanate prepared by obtaining a prepolymer containing cyanate groups A prepolymer containing a salt group. 17.3.3 to 10% by weight NCO content and polyester polyol , Hydroxyl-containing polycarbonate and polyoxytetramethylene glycol. Having a molecular weight of more than 800 and up to 3,500 selected from the group The polyhydroxyl compound is reacted with diphenylmethane 4,4'-diisocyanate To obtain an addition polymerization product containing urethane and isocyanate groups, and Reacting this with 3,3'-dimethylbiphenyl 4,4'-diisocyanate Prepared by obtaining a prepolymer containing isocyanate groups. Socyanate group-containing prepolymer. 18. (A) or the hydroxyl group of (a) and (b) versus diphenylmethane 4,4'-di NCO groups of isocyanate versus 3,3'-dimethylbiphenyl 4,4'-diisocy The equivalent ratio of NCO groups of anate is 1:> 1-6: 0.02-6. Item 18. An isocyanate group-containing prepolymer according to item 16 or 17.